Dyestuffs and process of making same



Patented Apr. 24, 1928.

- UNITED I STATES PATENT OFFICE.

FRITZ STRAUB, OF BASEL, AND HERMANN SCHNEIDER, OF RIEHEN, NEAR BASEL,SWITZERLAND, ASSIGNORS TO THE FIRM SOCIETY'OF CHEMICAL INDUSTRY 111'BASLE, 0F BASEL, SWITZERLAND.

DYESTUFFS AND PROCESS OF MAKING SAME.

No Drawing. Application filed March 12, 1926, Serial No. 94,317, and inSwitzerland March 28, 1925.

The present invention relates to new azo dyestuffs containing metalsvaluable for the production of fast tints 0n the fibre. It comprises thenew dyestsufi's, the process of making the same,- and the material dyedwith the new'dyestufis.

It has been found that new azo dyestuffs containing metals may beobtained by treating azo dycstufl's corresponding with' the generalformula:

llOiS (1)1! l! wherein the ys stand for hydrogen atoms which arereplaced at least once and at most twice by sulfogroups which latter'are not adjacent to each other and of which at least one is in 3 or4-position, R meaning the residue of a coupling component having atleast two nuclei such as naphthalene or phenylmethylpyrazolonederivatives, with agents yielding metals, such as copper, nickel, cohaltor chromium compounds.

The new dyestufis containing metals, which are to be considered as comlex metal compounds of the azo dyestuffs of the above indicated generalformula, form reddish brown to blackish powders, dissolving in water andin dilute caustic soda solution with orange to brown, red-violet, blueand blackish coloration, yielding on wool, when dyed from an acid bath,red to violet, blue and black tints.

' The azo dyestuffs used as parent material in this inventioncorresponding with the general formula:

H018 OH wherein R and the ys have the above indicated meaning, arepartially known and may be obtained by reaction of diazo compounds ofthe 2:1-aminonaphthol4r8 or 3:8-disulfonic acids with all kinds ofcoupling components.- If the coupling is realized in the usual manner,i. e. in more or less concentrated solution alkaline with caustic soda,dyestuffs are obtained, but their format(i1on takes place very slowlyand with bad yiel i It has now been found that, by carrying out thecoupling in presence of concentrated caustic potash solution, theformation of the dyestutf occurs very rapidly and with excellent yield.The technical manufacture of the dyestuffs which are the subject matterof the present invention has thus only been made possible by thediscovery of the coupling process herein disclosed.

Example 1.

Into a mixture of 56 parts of caustic potash, 46 parts of water and 15parts of B- nuphthol there are introduced, while stirring, at about 50,parts of the diazo compound of Z-amino-l-hydroxynaphthalene-4:8disulfonic acid in form of a paste of 55.5% strength. The whole isstirred for some time at the same temperature until disparition of thediazo compound, diluted with 300 parts of water, neutralized with nottoo dilute mineral acid and the dyestuif cor-responding with theformula:

SOaH OH OH precipitated with common salt. It forms a dark powder,dissolving in dilute acetic acld and dilute caustic soda solution withblue red, in dilute soda solution with cyaneous and in concentratedsulfuric acid with violet coloration. It yields on wool blue-red tintschanging by afterchroming to blue with partial destruction of thedyestufi, and to violet by after-coppering. The isomeric dyestulf froma-naphthol dissolves in dilute acetic acid and dilute caustic sodasolution with bluish-red and red-violet, in dilute soda solution withviolet coloration, in concentrated sulfuric acidwith blue coloration;the dyestufls from 2:3-hydroxynaphthoic acid or 3-hydroxynaphthaIene-1:S-dicarboxylic acid 'ssolve also with red-violet and blue-violetcoloration in dilute acetic acid, and in dilute caustic soda solutionwith blue, in dilute soda solution and in concentrated sulfuric acidwith violet to blue coloration. Their afterchromed dyeings on wool areli ht blue owing to strong destruction of the yestufi,

their aftercoppered dyeings are violet.

' Example 2.

Into a mixture of. 56 parts of caustic potash, 46 parts of water and 32parts of l-hydroxynaphthalene-3: 8-disulfonic acid there are introduced,while stirring, at about parts of the diazo compoundOfQ-aminol-hydroxynaphthalenetz 8-disulfonic acid in 'form of a paste of55.5% strength. Thewhole is stirred for some time at the sametemperature until disparitiori of the diazo compound, diluted with 300parts of water, neutralized with not too dilute mineral acid andl thedyestufi corresponding with the formu a:

scar on on son:

lene-3: 8- or4: 8-disulfamide, analogous dye-, stufis are obtained,dissolving in dilute acetic' acid with red to blue-red, in dilutecaustic soda solution with red-violet to blue-red, in dilute sodasolution with red-violet to greenblue, and in concentrated sulfuric acidwith red-violet to blue-red coloration, the aftercoppered dyeings 0nwool being red to blue violet, the afterchromed dyeings being light blueto green-blue.

' Example 3.

Into a mixture of 56 parts of caustic potash, 46 parts of water and 18.3parts of 1- phenyl-3-methyl-5-pyrazolone there are introduced, whilestirring, at about 80, 60

parts of the diazo compound of 2-amino-1-hydroxynaphthalene3;8-disulfonic acid in form of a paste of 55.5%strength. The whole is stirred for-some time at the same temperatureuntil disparition of the diazo compound, diluted with 300 parts ofwater, neutralized with not too dilute mineral acid and the dyestutlcorresponding with the formula 4 soar on n o son! 5 precipitated withcommon salt. The new dyestutl forms a reddishbrown powder, dissolving inwater with orange and in dilute caustic soda solution with reddishbrangecoloration, yielding on wool orange tints which change to red byafterchroming.

By replacing this pyrazolone derivative by the barbituric acid ananalogous dyestuli' is obtained'dissolving in dilute acetic acid withorange, in dilute caustic soda solution with red, in-concentratedsulfuric acid with orange coloration. It yields on wool orange tintswhich change to red by afterchroming,

to red-brown by aftercoppering. The corresponding dyestufi fromresorcylic acid forms a brown-red powder, dissolving in diluteacetic-acid with red, in dilute caustic soda solution with black-violet,in concentrated sulfuric acid with blue-red coloration, dyeing wool redtints which are destroyed by afterchroming and become red-violet byaftercoppering.

Example 52.6 parts of the dycstufi' from th diazo compound ofQ-amino-l-hydroxym phthalene-4.8-disulfonic acid and l-p enyl-3-methyl-5-pyrazolone are dissolved n 2000 parts of boiling water. To thissolution there are added 21 parts of copper sulfate, dissolved in 300parts of boiling water. The whole is boiled for some time, whileneutralizing the free mineral acid with sodium acetate. he now dyestufi'containing copper is then salted out. It forms an orange powder,dissolving in water and dilute caustic soda solution with redcoloration, dyeing wool redtints.

The copper compounds of the dyestuffs of the Example 3 or of theisomeric dycstulis from the Z-amino-l-hydroxynaphthalcne- 3:8-disulfonicacid dissolve in waterand in dilute caustic soda solution with orange tobrown and bluish-red coloration, dyeing wool reddish-brown to violettints.

The corresponding chromium compounds dye wool bluish-red to violettints.

Example 5. 67.8 parts of the dyestufi from the diazo compound ofQ-amino-l-hydroxynaphthalene-4.8-disulfonic acid and l-hydroxynapharedissolved in 1500 parts of boiling water. To this solution there areadded 21 parts of copper sulfate dissolved in 300 parts of boilingwater, the whole is boiled for some time, while neutralizing theliberated mineral acid with sodium acetate. The dyestutf containingcopper thus obtained is then salted out. It forms a dark powder,dissolving in water and in dilute caustic soda solution with redvioletcoloration and dyeing wool from an acid bath red-violet fast tints. Thedyestufi's of the Examples 1 and 2 yield copper derivatives dyeing woolalso violet to blueviolet fast tints, those of Example 3 yield on woolby the same treatment red to red-brown tint-S.

The cobalt and nickel compounds of these dyestuffs, which are formed inthe same manner, but using nickel sulfate or cobalt sulfate instead ofcopper sulfate, dye wool claret to reddish violet.

Example 6'.

49.7parts of the dyestuff from diazotized 2-amino 1 hydroxynaphthalene 48-disulfonic acid and B-naphthol are introduced into a solution ofalkali metal chromite obtained by treating 100 parts of achromiumhydroxide hydrate paste, corresponding with 17.4 parts of C50,,with 60 parts of potash and heating until a clear solution is formed.The mass is then heated at 80 until the whole chromium has been taken upby the azo dyestuff. The reaction mixture is then diluted with water,neutralized with mineral acid and the dyestufl' thus obtained salted outwith common salt. It forms a dark pow der, dissolving in water withblue, in dilute caustic soda solution with red-violet coloration,yielding on wool, when dyed from an acid bath, fast navy-blue tints.

Similar products are obtained if instead of alkali metal chromitechromium fluoride, chromium acetate or formate or chromium hydroxidehydrate are employed as agents yielding chromium.

The isomeric dyestufl' containing chromium from a-naphthol showsanalogous prop erties.

Very similar are also the properties of the isomeric dyestuffs from the2-amino-1- hydroxynaphthalene-3 8-disulfonic acid.

The other dyestuffs of Example 1 from 2:3-hydroxynaphtholic acid andfrom hydroxynaphthalene-l 8-dicarboxylic acid yield chromium compoundsdissolving in water with violet and green-blue, in dilute caustic sodasolution with red-violet and violet coloration. They yield on wool whendyed from an acid bath and when printed on cotton fast blue tints.

Example 7.

67.8 parts of the dyestufi' from the diazo compound of2-amino-l-hydroxynaphthalene-4: 8-disulfonic acid andl-hydroxynaphthalene-3:S-disulfonic acid are dissolved in 1500 parts ofboiling water. To the solution thus obtained there are added 20 parts ofchromium oxide in form of a chromium fluoride solution, the whole beingheated together in the presence of glass powder until the dyestutfcontaining chromium is formed. Thedyestutl' solution is thenconcentrated by evaporation and the new dyestutf is obtained bycrystallization or by salting out. It forms a dark powder, dissolving inwater with blue, in dilute caustic soda solution with violet coloration,yielding on wool, when dyed from an acid bath, blue tints. The dyes-tuftdescribed in Example 2 yields chromium compounds showing similarproperties, i. e. they dissolve in water with blue to green-blue, indilute caustic soda solution with violet coloration, yielding on wool,when dyed from an acid bath, fast blue tints.

\Vhat we claim is:

1. As a step in the production of complex metal compounds of thedyestuffs corresponding with the general formula:

wherein the ys stand for hydrogen atoms which are replaced at least onceand at most twice by sulfogroups which latter are not adj acent to eachother and of which at least one is in 3 or 4-position, R meaning theresidue of a coupling component having at least two nuclei, the hereindescribed process which consists in the coupling of the diazotizedaininohydroxynaphthalene disulfonic acids corresponding with the generalformula:

HOiS OH wherein the ys stand for hydrogen atoms which are replaced atleast ,once and at most twice by sulfogroups which latter are not adjacent to each other and of which at least one is in 3 or.-4-position,with a coupling component having at least two nuclei in a highlyconcentrated caustic potash; medium. 2. As a step in the production ofcomplex metal compounds of the dyestuffs corresponding with the generalformula: 1

wherein the ys stand for-hydrogen atoms which are replaced at least onceand at most twice by sulfogroups which latter are not adj acent to eachother and of which at least one is in 3 or 4-position, R meaning aresidue of any hydroxynaphthalene compound, the herein described processwhich consists in the coupling of the diazotizedaminohydroxynauhthalene-disulfonic acids corresponding with the generalformula:

i H018 on wherein the stand for hydrogen atoms which are replaced atleast once and at most twice by sulfogroups which latter are notadjacent to each other and of which at least one isin 3 or 4-position,with any hydroxynaphthalene compounds in a highly concentrated causticpotash medium.

3. 'As a step in the production of complex.

metal compounds of the dyestuffs corresponding with the general formula:

b os wherein R stands for a residue of any hydroxynaphthalcne compound,the herein described process which consists in the coupling of thediazotized aminonaphthol-disultonic acid corresponding with the formula:

son; on

with any liydroxynaphthalene compounds in a highly concentrated causticpotash medium.

4. As a step in the production of complex metal compounds of the azodyestutf corre sponding with the formula:

son; on on the herein described process which consists in the couplingof diazotized 2: l-aminohyaroxynapnthalenetz 8-disulfonic acid withB-naphthol in a highly concentrated caustic potash medium.

-5. As a step in the production of complex metal compounds of the azodyestutl's correspending with the general formula:

H013 (llli N=N-R wherein the ys stand for hydrogen atoms which arereplaced at least once and at most twice by sulfogroups which latter arenot;

adjacent to each other and of which at least one is in 3 or i-position,R meaninga residue of a coupling component having at least two nuclei,the herein described process which consists in the treatment of the azodyestufis corresponding with the. above explained general formula, withtrivalent compounds of chromium.

(i. As a step in the roduction of complex metal compounds of the azodyestutl's corresponding with the. general formula:

Hols on OIHI wherein R stands for a residue of any hy-' izodroxynaphthalene compound, the herein described process which consistsin the treatment of the azo dyestuffs corresponding with the aboveexplained general formula, with trivalent compounds of chromium.

8. As a step in the production of complex metal compounds of the azodyestufi' corresponding with the formula:

$0111 on on S0111 the herein described process which consists in thetreatment of these azo dyestutl's with trivalent compounds of chromium.

9. As new azo dyestufi's containing metals, the herein described complexchromium compounds of the azo dycstutfs corresponding with the generalformula:

HOIIS OH wherein the 3/5 stand for hydrogen atoms which are replaced atleast once and at most twice by sulfogroups which latter are not adjacentto each other and of which at least one is in 3 or 4-position, Rmeaning a coupling component having at least two nuclei which productsform reddish-brown to blackish powders, dissolving in water and indilute caustic soda solution with orange to brown, red-violet, blue andblackish coloration, and yielding on wool, when dyed from an acid bath,red to violet, blue and black fast tints.

10. As new azo dyestuffs containing metals the herein described complexchromium compounds of the azo dyestufl's corresponding with the generalformula:

wherein the ys stand for hydrogen atoms which are replaced at least onceand at most twice by snlfogroups which latter are not adjacent to eachother and of which at least one is in 3 or 4-position, R meaning aresidue of any hydroxynaphthalene compound, which products form blackishpowders, dissolving in water with violet to green-blue, in dilutecaustic soda solution with red-violet to violet coloration, yielding onwool. w n dyed from an acid bath, fast blue tints.

11. As new azo dyestuffs containin r metals the herein described complexchromium compounds of the azo dyestutl's of the general formula SOiH Ollwherein R stands for a residue of any hydroxynaphthalene compound, whichproductsv form blackish powders, dissolving in water with violet togreen-blue, in dilute caustic soda solution with red-violet to violetcoloration, yielding on wool, when dyed from an acid bath, fast bluetints."

12. As new azo dyestuffs containing metals the herein described complexchromium compounds of the azo dyestutf corresponding with the formulaSOaH OH OH OzH with the dyestuffs of with the dyestnfi's of FRITZSTRAUB. HERMANN SCHNEIDER.

